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首页> 外文学位 >Synthesis of Novel Fused Tricyclic and Tetracyclic Skeletons Through Rhodium(I)-Catalyzed [2+2+2+1] Cycloaddition of Enediyne Derivatives with Carbon Monoxide.
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Synthesis of Novel Fused Tricyclic and Tetracyclic Skeletons Through Rhodium(I)-Catalyzed [2+2+2+1] Cycloaddition of Enediyne Derivatives with Carbon Monoxide.

机译：铑（I）催化烯属衍生物与一氧化碳环加成的[2 + 2 + 2 + 1]环加成反应合成新颖的稠合三环和四环骨架。

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摘要

Natural products (NP) and their metabolites isolated from diverse origins have been an extraordinary source of active pharmaceuticals, agrochemicals and other applications. Often, (NP) also serve as templates to obtain more potent and selective agents through structure-activity relationship (SAR) studies. A ubiquitous feature of (NP) and their metabolites is that they often contain fascinating fused-ring skeletons. Unfortunately, the vast majority of (NP) cannot be isolated in large quantities from their natural source. Consequently, the need to develop highly efficient synthetic methods that provide access to fused ring-skeletons with handles for further modification is necessary. Transition metal-catalyzed carbocyclization and cycloaddition reactions have proven to be among the most efficient methods for (NP) synthesis as well as constructing "natural product-like" (NPL) and "drug-like" (DL) skeletons.;As part of ongoing studies by the Ojima lab into transition metal catalyzed carbocyclizations and higher-order cycloaddition reactions, the Rh(I)-catalyzed [2+2+2+1] cycloaddition of enediyne derivatives was investigated. The reaction of cyclohexene-diynes in the presence of [Rh(CO)2Cl]2 and CO (2 atm) gave novel 5-7-6-5 fused tetracyclic products while the reaction of cyclopentene-diynes under similar conditions gave the corresponding 5-7-5-5 fused tetracyclics in good to excellent yields. In addition to the expected products, the diene shifted regioisomers were obtained for all 1-silyl-substituted cycloalkenyl-diyne substrates investigated. gamma-Butyrolactones are prominent constituents in a diverse class of biologically active compounds. Thus, the Rh(I)-catalyzed [2+2+2+1] cycloaddition of 1-methyl-dodec-11-ene-8-oxo-1,6-diynes which afforded 5-7-5 tricyclic products with fused gamma-butyrolactones was also investigated. The reaction variables as well as the mechanism for the formation of these fused products are presented.
机译：从各种来源分离的天然产物（NP）及其代谢产物一直是活性药物，农用化学品和其他应用的非凡来源。通常，（NP）还可作为模板，通过结构-活性关系（SAR）研究获得更多有效和选择性的药物。 （NP）及其代谢物的普遍特征是它们通常包含迷人的稠环骨架。不幸的是，绝大多数（NP）不能从其天然来源中大量分离出来。因此，需要开发一种高效的合成方法，该方法可提供带有手柄的稠合环骨架以进行进一步修饰。过渡金属催化的碳环化和环加成反应已被证明是用于（NP）合成以及构建“天然产物样”（NPL）和“药物样”（DL）骨架的最有效方法之一。在Ojima实验室正在进行的过渡金属催化的碳环化和高阶环加成反应研究中，研究了Rh（I）催化的烯二炔衍生物的[2 + 2 + 2 + 1]环加成反应。在[Rh（CO）2Cl] 2和CO（2 atm）存在下，环己烯-二炔的反应生成了新颖的5-7-6-5稠合四环产物，而环戊烯-二炔在相似条件下的反应得到了相应的5 -7-5-5稠合的四环化合物，收率良好。除了预期的产物外，对于所有研究的1-甲硅烷基取代的环烯基-二炔底物，均获得了二烯移位的区域异构体。 γ-丁内酯是多种生物活性化合物中的重要成分。因此，Rh（I）催化的1-甲基-十二-十一-烯-8-氧代-1,6-二炔的[2 + 2 + 2 + 1]环加成反应提供了5-7-5稠合的三环产物还研究了γ-丁内酯。介绍了反应变量以及形成这些熔融产物的机理。

著录项

  • 作者

    Kaloko, Joseph Junior.;

  • 作者单位

    State University of New York at Stony Brook.;

  • 授予单位 State University of New York at Stony Brook.;
  • 学科 Chemistry General.;Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2010
  • 页码 327 p.
  • 总页数 327
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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